Aryl-azo-pyridone compounds containing a substituted pyrimidine or triazine group

ABSTRACT

1. A WATER-SOLUBLE MONOAZO DYESTUFF OF THE FORMULA   (1-Z,2-(O=),3-T2,4-TI,5-((HO3S)3-(A)-N=N-),6-(HO-)-1,2-   DIHYDROPYRIDINE)-NH-(N&lt;(-CH2-X=C(-)-N=CH-)(-CL)(-Q1-R1-   Q2-R2)   WHEREIN A REPRESENTS BENZENE OR NAPHTHALENE, Z REPRESENTS HYDROGEN, LOWER ALKYL, HYDROXYETHYL, CYCLOHEXYL OR PHENYL, T1 REPRESENTS HYDROGEN, HYDROXYL OR LOWER ALKYL, T2 REPRESENTS HYDROGEN, LOWER ALKYL, CARBAMOYL OR CYANO, Z REPRESENTS LOWER ALKYL OR PHENYL, THE -NH-GROUP IS DIRECTLY ATTACHED TO A OR TO Z, X REPRESENTS =N-,   -CO-X-CO-   Q1 REPRESENTS OXYGEN, SULPHUR OR -NH-, Q2 REPRESENTS OXYGEN OR A DIRECT BOND, R1 REPRESENTS ETHYLEEN, PHENYLENE OR CYCLOHEXYLENE, AND R2 REPRESENTS ALKYL HAVING 2-15 CARBON ATOMS, BENZYL, PHENYL OR CYCLOHEXYL, SUC THAT R1 AND R2 TOGETHER CONTAIN AT LEAST 8 CARBON ATOMS.

United States Patent 3,847,894 ARYL-AZO-PYRIDONE COMPOUNDS CONTAIN- INGA SUBSTITUTED PYRIMIDINE OR TRI- AZINE GROUP Denis Robert AnnesleyRidyard, Manchester, England,

assignor to Imperial Chemical Industries Limited, London, England NoDrawing. Filed Apr. 25, 1972, Ser. No. 247,321

Claims priority, application Great Britain, Apr. 29, 1971,

2,121/ 71 Int. Cl. C09!) 29/36 U.S. Cl. 260-153 3 Claims ABSTRACT OF THEDISCLOSURE A water-soluble azo dyestutf having the general formula:

wherein A represents the residue of a diazo component of the benzene ornaphthalene series, Z represents a hydrogen atom or an optionallysubstituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, Trepresents a hydrogen atom, an optionally substituted alkyl, aralkyl,cycloalkyl, aryl or heterocyclic radical or a hydroxyl, cyano, -COR--OCOR or CONR R group in which R and R each independently represents ahydrogen atom or an optionally substituted alkyl, aralkyl, cycloalkyl,aryl or heterocyclic radical or the group N'R R represents the radicalof 5 or 6 membered heterocyclic ring, T 2 represents a hydrogen atom, anoptionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclicradical or a cyano, -COR COOR or -CONR R group in which R and R have themeanings already stated, X represents =N--, =C-Cl or =C-CN, Y representchlorine or bromine, Q represents oxygen, sulphur or NR wherein Rrepresents hydrogen or lower alkyl, Q represents oxygen, sulphur or adirect link, R represents an optionally substituted alkyl radical havingfrom 2 to 18 carbon atoms or a cycloalkyl, aralkyl or aryl radical, Rrepresents a divalent hydrocarbon radical such that R and R togethercontain at least 8 carbon atoms and n represents a positive integer, thedyestutf being free from nitro groups.

This azo dyestutf, containing fiber-reactive groups, are valuable forcoloring polyamide textile materials and have excellent fastness to wettreatments and to light.

This invention relates to azo dyestuifs and more particularly it relatesto water-soluble azo dyestuffs containing fibre-reactive groups whichare particularly valuable for coloring polyamide textile materials.

Heretofore, there have been known water-soluble compounds containing atleast one sulphonic acid group, at least one cellulose-reactive groupand at least one group of the formula:

HO N -O wherein Z represents a hydrogen atom orvan alkyl, aralkyl,cycloalkyl, aryl or heterocyclic radical which may be substituted.

3,847,894 Patented Nov. 12, 197 1- ice T represents a hydrogen atom, aCN, COOR CONR R COR or CH group or an alkyl, aralkyl, cycloalkyl, arylor heterocyclic radical which may be substituted, and R and R eachindependently represents a hydrogen atom, an alkyl, aralkyl, cycloalkyl,aryl or heterocyclic radical which may be substituted or the group NR Rrepresents the radical of 5 or 6 membered heterocyclic ring compound,

T represents a hydrogen atom, a CN, COOR CONR R or COR group or analkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical which may besubstituted, and M represents a hydrogen atom or a metal atom formingpart of a metal-complex system in the dyestufi.

The present invention provides water-soluble azo dyestuffs having thegeneral formula:

wherein A represents the residue of a diazo component of the benzene ornaphthalene series, Z represents a hydrogen atom or an optionallysubstituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, Trepresents a hydrogen atom, an optionally substituted alkyl, aralkyl,cyclo alkyl, aryl or heterocyclic radical or a hydroxyl, cyano, -CORCOOR or 'CONR R group in which R and R each independently represents ahydrogen atom or an optionally substituted alkyl, aralkyl, cycloalkyl,aryl or heterocyclic radical or the group -NR R represents the radicalof a 5 or 6 membersd heterocyclic ring, T represents a hydrogen atom, anoptionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclicradical or a cyano, --COR -COOR or CONR R group in which R and R havethe meanings already stated, X represents =N,

Y represents chlorine or bromine, Q represents oxygen, sulphur or NR--wherein R represents hydrogen or lower alkyl, Q represents oxygen,sulphur or a direct link, R represents an optionally substituted alkylradical having from 2 to 18 carbon atoms or a cycloalkyl, aralkyl oraryl radical, R represents a divalent hydrocarbon radical such that Rand R together contain at least 8 carbon atoms, and n represents apositive integer, the dyestutfs being free from nitro groups.

The radical represented by A may carry the usual substituentsappropriate to diazo components. Examples of such substituents includesulphonic acid and carboxylic acid groups, chlorine, bromine, cyano,lower alkyl, lower alkoxy, trifluoromethyl, --NHCOR where R is an alkyl,aryl, alkoxy, aryloxy, alkylamino, arylamino or amino radical, SO NR R"where R is alkyl or aryl and R is hydrogen or alkyl and AO R where R isalkyl or aryl. Other substituents which may be carried by A includephenylazo and naphthylazo radicals which may themselves be substituted.

The optionally substituted alkyl radicals represented by T T R R and Zare preferably optionally substituted lower alkyl radicals, and asspecific examples of such radicals there may be mentioned methyl, ethyl,npropyl and n-butyl, hydroxy lower alkyl such as B-hydroxyethyl, loweralkoxy lower alkyl such as B-(methoxy or ethoxy) ethyl, cyanomethyl,carbamoylmethyl, carbethoxymethyl and acetylmethyl.

Throughout the Specification the terms lower alkyl and lower alkoxy areused to denote alkyl and alkoxy radicals respectively containing from 1to 4 carbon atoms.

Divalent hydrocarbon radicals which may be represented by R includearylene radicals optionally carrying one or more halogen, alkyl oralkoxy substituents, alkylene radicals and cycloalkylene radicals.

When R represents an alkyl radical, it may be branched or straightchain; preferably it contains from 4 to 12 carbon atoms.

As examples of aralkyl radicals represented by T T R R R and Z there maybe mentioned benzyl and p-phenylethyl. As an example of cycloalkylradicals represented by T T R R R and Z, there may be mentionedcyclohexyl. The optionally substituted aryl radicals represented by T TR R R and Z are preferably optionally substituted phenyl radicals and asspecific examples of such radicals there may be mentioned phenyl, tolyl,chlorophenyl, carboxyphenyl, methoxyphenyl and sulphophenyl. Theoptionally substituted heterocyclic radicals representsd by T T R R andZ are preferably optionally substituted 5- and 6-membered heterocyclicrings, and as specific examples of such radicals there may be mentioned2-pyridyl, 2-thiazolyl, l-piperidinyl and 1- morpholinyl.

As examples of 5 and 6 membered heterocyclic rings which may berepresented by NR R there may be mentioned piperidine, morpholine,piperazine and pyrrolidine.

Within the general class of dyestutfs represented by Formula I,particular mention may be made of those dyestuffs in which Q is oxygenor sulphur and R is an arylene radical optionally carrying one or morehalogen, alkyl or alkoxy substituents.

The positive integer represented by n is preferably 1 or 2.

Some of the dyestuffs of the invention can exist in a number oftautomeric forms; for convenience the dyestuffs have been formulated inonly one of these forms but it is to be understood that thisSpecification relates to dyestuffs in any of the possible tautomericforms.

A preferred class of monoazo dyestulfs of the invention comprises thedyestuffs which in one of the possible tautomeric forms are representedby the formula: II

wherein T T R R Q Q X, Y and n have the meanmeanings already stated andthe fibre-reactive group is attached to the benzene ring in meta or paraposition to the azo group.

A further preferred class of monoazo dyestuffs of the invention may berepresented by the formula: III

Tl I

HO O

lower alkyl such as methyl, lower alkoxy such as methoxy, cyano andacetyl amino.

The dyes of Formula I may be prepared by reacting a compound of theformula:

A. KN/J (IV) wherein X and Y have the meanings already stated, with, ineither order, an azo compound of the formula:

I NHz A-N=N' -'r :0

SO H n E J a (V) wherein A, T T Z and n have the meanings already statedand a compound of the formula:

wherein R R Q and Q have the meanings already stated.

The dyestuffs of Formula I may also be prepared by diazotizing anaromatic amine of the benzene or naphthalene series and coupling thediazo compound so obtained with a coupling component of the formula:

wherein T T and Z have the meanings already stated, the amine and thecoupling component together containing at least one sulphonic acid groupand a group of the formula:

I 1 17 X L x (vrn wherein X and Y have the meanings already stated, andthen reacting the product with a compound of Formula VI.

Suitable compounds of Formula IV are cyanuric chloride, cyanuricbromide, 2,4,6-trichloropyrimidine, 2,4,6- tribromopyrimidine, 2,4,5,6tetrachloropyrimidine and 2,4,6-trichloro-S-cyanopyrimidine.

Aromatic amines which contain a fibre reactive group of formula VIII canbe obtained by condensing a compound of formula IV with the appropriatediamine under such conditions that only one of the two amino groupsreacts with the compound of formula VIII. As specific examples of suchdiamines there may be mentioned 1,3- phenylenediamine 4 sulphonic acid,1,4-phenylenediamine 2 sulphonic acid, l,3-phenylenediamine-4,6-disulphonic acid, 1,4 phenylenediamine 2,5 disulphonic acid and2,6-diaminonaphthalene-4,8-disulphonic acid.

Coupling components of formula VII which contain a fibre reactive groupof formula VIII can be obtained by condensing the appropriate couplingcomponent containing an amino group with a compound of formula IV.

As specific examples of aromatic amines free from fibre-reactive groupswhich can be coupled with coupling components of formula VII whichcontain a fibre reactive group of formula VIII there may be mentionedaniline 2-, 3- and 4-sulphonic acids, aniline -2,5-, 2,4- and3,5-disulphonic acids, 2-aminophenol -4 or 6-sulphonic acid, 4- or5-sulpho -2-aminobenzoic acid, 4-(or 6-)chloro-2- aminophenol -6- (or4-)sulphonic acid, 2-aminophenol-4,6-disulphonic acid, 4-(acetylamin0 ormethyl or methoxy) aniline -2-sulphonic acid, l-naphthylamine -3-, 4-,5-, 6-, 7- and 8- sulphonic acid, 2-amino naphthalene -1-, 5-, 6-, 7- or8-sulphonic acid, l-naphthylamine, 2,7-, 3,6-, 3,8-, 4,6- and 4,7-disulphonic acid, Z-naphthylamine, 1,5-, 3,7-, 4,8-, 5,7- and6,8-disulphonic acid I-naphthylamine -36,8- 4,8-, 5,7- and6,8-disulphonic acid l-naphthylamine -3,6,8- and 2,5,7 trisulphonic acidand 2 naphthylamine 3,6,8- tri-sulphonic acid.

Azo compounds of Formula V may .be obtained by diazotizing an aromaticamine and coupling the diazo compound so obtained with a couplingcomponent of the formula:

Suitable compounds of Formula VI include alkylphenols, for example m-,and p-ethylphenols, 0-, m-, and pbutylphenols, amylphenols,hexylphenols, p-octylphenol, p-nonylphenol, p-dodecylphenol,m-pentadecylphenol, phexadecylphenol, and p-octadecylphenol;cycloalkylphenols, for example oand p-cyclohexylphenols; aralkylphenols,for example 0-, mand p-benzylphenols; arylphenols, for example 0-, m-,and p-phenylphenols; alkoxyphenols, for example hydroquinone andresorcinol monoalkyl ethers where the alkyl residue may be ethyl,propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl;cycloal-koxyphenols, for example p-cyclohexyloxyphenol, aralkoxyphenols,for example p-benzyloxyphenol; aryloxyphenols, for examplep-phenoxyphenol; thio-substituted phenols, for example 0-, m'-, andp-(butylthio)phenols, 0- and m-(hexylthio)phenols, o-(heptylthio)phenol,p-(dodecylthio)phenol, 0- and p-(benzylthio)phenols, 0-, m-, andp-(phenylthio)phenols; benzenethiols, for example p-butyl-benzenethiol,p-butoxybenzenethiol, p-(butylthio)benzenethiol, p-amylbenzenethiol,p-hexylbenzenethiol, p-hexyloxybenzenethiol, p-octylbenzenethiol,p-nonylbenzenethiol, p-decylbenzenethiol, p-dodecylbenzenethiol,p-biphenylenethiol, and m-(phenylthio) benzenethiol. Suitable compoundsof Formula VI wherein R may carry one or more halogen, alkyl, or alkoxysubstituents in addition to the -Q R residue include4-n-butyl-Z-methylphenol, 4--sec-butyl-2-methylphenol,3-is0-butyl-S-methylphenol, 4-n-butyI-Z-methoxyphenol,4-n-butyl-2-chlorophenol, 4-chloro-2-ethylphenol,

2,4- and 2,6-dipropylphenols, 2,4- and 2,6-di-tert-butylphenols,2,6-di-tert-butyl-4-ethylplrenol, 2,6-di-tert-butyl-4-chlorophenol,2,6-di-tert-butyl-4-methoxyphenol, 4-tert-butyl-Z,6-dimethylphenol,4-tert-butyl-Z,S-dimethylphenol, 4-tert-:butyl-2,S-dimethylphenol,4-tert-amyl-Z-methoxyphenol, 2-chloro-4-octylphenol.

Suitable compounds of formula VI also include alkylamines, for exampleoctylamine and dodecylamine, substituted alkylamines for examplebenzylisopropylamine and benzylsec butylamine, substitutedcyclohexylamines, for example 2-benzylcyclohexylamine and4-butylcyclohexylamine and alkylanilines for example 4-butylaniline,4-octyl aniline and 4-dodecylaniline.

The reactions leading to the formation of dyes of Formula I may becarried out using conditions that have been fully described in the priorart for such reactions.

The dyes of the present invention, optionally in the form of theirwater-soluble salts, particularly sodium salts, may be used for coloringcellulosic textile materials using methods that have been fullydescribed in the prior art for the application of monohalogenotriazinyland halogenopyrimidinyl dyes. They are particularly useful, however, forcoloring textile materials based on natural or synthetic nitrogenousfibres.

The dyes are especially suitable for dyeing wool including wool whichhas been rendered non-felting or machinewashable by chemical processessuch as acid chlorination, the use of hypochlorite under neutral orslightly alkaline conditions, the use of permonosulphuric acid, the useof the sodium salt of dichloroisocyanuric acid, and by the deposition ofpolymers on the surface of the wool using for exampleamine-epichlorohydrin resins. Material which has been so treated may bedyed by conventional wool dyeing methods, by the use of pad-batch dyeingmethods, and also by continuous pad-steam processes. When applied tosuch fibres, the dyes have excellent fastness to wet treatments and tolight.

The invention is illustrated but not limited by the following Examplesin which all parts are by weight.

Example 1 A solution of 6.7 parts of 1,3-phenylenediamine-4,6-disulphonic acid in parts of water at 0-5 C. and pH 5.0 is added rapidlyto a suspension prepared by dissolving 4.62 parts of cyanuric chloridein 15 parts of acetone and adding the resulting solution to 30 parts ofwater and 30 parts of ice. The mixture is stirred for 2 hours at 05 C.maintaining the pH at 45 by addition of 2N sodium carbonate solution asrequired. 7.5 parts of 36 Tw hydrochloric acid are then added and themixture diazotized by the addition of 1.7 parts of sodium nitrite in11.5 parts of water. The diazo suspension is then added to a solution of4.9 parts of 1-ethyl-3-aminocarbonyl-4-methyl-6-hydroxypyrid-Z-one in100 parts of water at 0-5 C. and pH 7.0. The mixture is stirred at 05 C.for 2 hours maintaining the pH at 7.0 by addition of 2N sodium carbonatesolution, and is finally stirred for 16 hours gradually warming to 20 C.The reaction mixture is then added slowly during 30 minutes to a stirredsolution of 4.2 parts of p-tert-butyl phenol in a mixture of 50 parts ofacetone and 100 parts of water at 30 C., which has been adjusted to a pHbetween 8.5 and 9.0 by the addition of 2N sodium hydroxide solution. ThepH of the reaction mixture is maintained between 8.5 and 9.0 during theaddition. The reaction mixture is stirred under these conditions duringa further 3 hours and the pH is then adjusted to between 6.5 and 7.0.Sodium chloride (10% weight/volume) is then added and the precipitateddyestuff is filtered off, washed with 10% brine solution and dried at 40C.

When applied to wool from a weakly acid dyebath the dyestuif yields abright greenish yellow shade having excellent fastness to wet treatmentsand to light.

Example 2 If the 4.2 parts of p-tert-butylphenol in the above example isreplaced by 4.2 parts of 4-butylaniline and the reaction is carried outat pH 5-6, a dyestuff is obtained, which when applied to wool from aweakly acid dyebath yields a bright greenish yellow shade havingexcellent fastness to wet treatments and to light.

The following Table gives further examples of the invention obtained ina similar manner to Examples 1 and 2 by condensing the diamine named inthe second column with one mole of the acid chloride compound named inthe first column and diazotizing and coupling the resultant aminocompound with the coupling component named in the third column followedby condensation with the phenol, amine or thiol named in the fourthcolumn. The shade of the dyestulf when applied to wool or nylon is givenin the final column.

Example I II III IV Shade 3 Cyanuric chloride 1,3-phenylene diamine 4,6-1-ethy1-3-aminocarhonyl-4- 4-nonylphenol Grconishdisulphonic acid.methy1-6-hydroxypyrid-2- yellow.

one.

do 4-dodcoylphenol Do. 1-methyl-3-aminocarbonyH- 4-nonylphenol..- Do.

methyl-G-hydrcxypyrid-2- one. .do 3-pentadecylpheno1- Do. .do "do4-cycl0hexylphenol- Do.

1,4-phenyle a, 1-ethy1-3-aminocarbonyl-4- 4-nonylphenolReddishdisulphonic acid. methyl-fi-hydroxypryld-Z- yellow one.

. 4-benzylpheno1 Do. 4-phenoxy phenol Do. 4-11-butyl-2-methylpl1eno Do.ethy lnocarbonyl 4-dodecylphenol Do. methyl-6-hydroxypyrid-2- one.1,3phenylenediamine-4,6- l-ethy1-4-niethy1-0-hydroxy- 4-nonpylphenol. D

disulphonic acid pyrid-Z-one.

d .do 4-dodecylphenol D0. do. 1eth A-methyl-Iicyano-fi- 4-nonylphenolDe.

hydroxypyrid-Z-one. do l-othyl-3,4dimethyl6- 4-tert.-butylphenol Do.

hydroxypyrid-2-one. do. 1-ethyl-4-methyl-3cthyl-6- 4-nonylphenol. Do.

hydroxypyrid-Z-one. do l-ethyl-4-methyl-3-butyl-6- 4-tert.butylphenolDo.

hydroxypyrid-Z-one. d 2,6-dihydroxy-3eyano-4- 4-nonylphenol Do.

methylpyridine. do do l-B-hydroxyethyl-3-cyano-4- do Dmethyl-B-hydroxypyrid-Z- one. 2,6-dihydroxypyridine D2,6-dihydroxy4-methyl- D pyridine. 2,6-dihydroxy-3,4-di1nethyl do Do.

pyridine. 24 do l,4-diaminobenzeno-2,5- l-ethyli-methyl-fi-hydroxy- 4nonylplienol Roddjshdisulphonic acid. pyr1d-2-one. yellow. 25 do dol-ethy14-methyl-3-cyan0 4-octylphcnol D0.

G-hydroxypryid-Z-one. 26 do do. 2,6-dihydr0xypyridino 4-dodceylphenol D27 do do 2,6-dilivdr0xy-4-met11ylttorthutylphenol D0.

pyridine. 28 ,do do 1-cycl0heXyl-3cyano4- 4-ethy1phenol Dmethyl-B-hydroxypyrid-Z- one. 29 do do 2,4,6-trihydrpxypyridino.. 4nonylphenol D 30 do 2,G-diaminonaphthalene4,8- l-ethyl-3-ammocarbonyl-4-tert.butylpheno1 Orange,

disulphonic acid. i-methyl-fi-hydroxypyrid- -one.

31 do 1,3-phenylenediaminc-4,6- .d0 4-hexylbenzenethiol Gr ni h.

disulphonic aeid. yellow. 32 do do l-e hy1-4-methy1-3-etl1y1-6-4-nonylbenzenethiol D hydroxypyrid-2one. 33 do "dol-ethyHmmthyI-B-hydroxy- 4-phenylphenol DJ,

pyrid-2-one d Q-phcnylphenol Do. 4-amylphenol Do. 4-octylphenol Do.

Oetylamine Do. 4-butylcyclohexylamine Do. Z-bonzylcyelohexylaxnine Do. 04-dodecylaniline D0. 41 y 4-butylaniline Do. 422,4,5,6-tetraoliloropyrirn .do Do. 43 2,4,6-trielilorofi5-eyanodo Dpyrimidine. 44 Cyanurie chloride 2-pheny1ethylamine Do. 45 .do2-phcnoxyethylaniine Do. 4 d 4-aminodiphenyl Do.

Example 47 C. for 3 hours, keeping the pH at 6 by the addition of 2Nsodium carbonate solution as required. The reaction mixture is thenadded during 30 minutes to a stirred solution of 13.2 parts of 4-nonylphenol in 100 parts of acetone at 30 C. The pH of the reaction mixtureis maintained between 8.5 and 9.0 during the addition. The reactionmixture is stirred under these conditions during a further 3 hours andthe pH is then adjusted to between 6.5 and 7.0. Sodium chloride (10%weight/volume) is then added and the precipitated dyestutf is filteredoif, washed with 10% brine solution and dried at 40 C.

When applied to wool from a weakly acid dyebath the dyestuff yields abright greenish yellow shade having excellent fastness to wet treatmentsand to light.

A suspension of 10.55 parts of N-B-aminoethyl-3- aminocarbonyl-4-methyl6 hydroxypyrid-Z-one in 100 parts of water is stirred at 40 C. anddissolved by addition of 2N sodium carbonate solution until solution isjust complete. The pH of the solution is then adjusted to 7.5 with 2Nhydrochloric acid and the solution is added during 15 minutes at pH 6.5and 0-5 C. to a suspension prepared by adding a solution of 10 parts ofcyanuric chloride in 30 parts of acetone to a mixture of 75 parts of iceand 75 parts of Water. The mixture is stirred at 0-5 C. for a further 2hours maintaining the pH at 6-7 by the addition of 2N sodium carbonatesolution as reuired. q A solution of 12.7 parts ofaniline-2,5-disulphonic acid h follmvmg F desfcrfbes further eXamP1e5 0fin 150 parts of water and 10 parts of 36 Tw hydro hl i the lnventionobtained in a similar manner by condensing acid is diazotized at 0-5 0.by the addition of 2N sodium the Pyndone 0r py compound named n C lumnnitrite solution until a faint excess of nitrous acid persists. I withCyamlric chloride, Coupling the resultant Product The excess of nitrousacid is removed by addition of a With the diazonium salt Of the aminenamed in Column 10% aqueous solution of sulphamic acid and the solutionII and finally reacting with the phenol or amine named is added to thecoupling solution prepared as described in Column III. The shade of thedyestuff when applied in paragraph one above. The mixture is stirred at10 to wool or nylon is given in the final column.

Example I II III Shade 48 l-B-aminoethyl-3-mninocarbonyll-methyl-fi-Aniline-2,5-disulphonic acid 4-d0decylanilineGreenishhydroxypyrid-2-one. yellow. 49 do2-naphthylamine-1.5-disulphonic acid 4-nenylphenol Yellow. 50 do2-naphthylamine-4,8-disulphonic acid 4-buty1phenol Do. 51l-fl-aminoethylA-methyl-fi-hydroxypyrid-Z-one do do Git-:(filiShe OW.2-naphthylamine-l,5-disulphonic acid .do y D0. 4-nonylphenol- Do.4-butylaniline. Do. 55 ..do-. 4-nonylphenol Do. 56.1-fi-aminoethyl-3,4-dimethyl'6-hydroxypyrid-2-0ne d0 do Do. 57--. d02-naphthylamine-1,5-disulphonic acid o D0, 58 do .d0 4-butylphenol Do.59 do 2-naphthylamine-4,8-disulphonic acid do Do. 60 1-3-amir10ethyl-3-cyan0-4-methyl'6-hydr0xypyrid- Aniline-2,5-disulphonicacid 4-nonylphenol Yellow.

2-one. 61 dn 2-naphthylamine-1,5-disulphonie acid 4-butylani1ineRedgishye ow. 62 1-(3-amlnophenyl)-3-cyano-4-methyl-G-hydroxy-Aniline-2,5-diSu1ph0nic acid 4-bntylpheno1 Greenish- 2-one. yellow.

What we claim is: 1. A water-soluble monoazo dyestuif of the formula l Tl l i 1 2 Rz wherein A represents benzene or naphthalene; Z representshydrogen, lower alkyl, hydroxyethyl, cyclohexyl or phenyl; T representshydrogen, hydroxyl or lower alkyl; T represents hydrogen, lower alkyl,carbamoyl or cyano;

Z represents lower alkyl or phenyl; the NH- group is directly attachedto A or to Z; X represents =N,

wherein T T Z, Q Q R and R have the meaning given in claim 1.

3. The water-soluble monoazo dyestutf of claim 1 of the formula whereinT T R R Q Q X and A have the meaning given in claim 1 and m is aninteger of 2-6.

References Cited UNITED STATES PATENTS 3,658,783 4/1972 Knobloch et a1.260153 3,455,897 7/1969 Barben 260146 3,709,869 1/1973 Mazza 260-453OTHER REFERENCES Wagner et a1., Synthetic Organic Chemistry, John Wiley0 & Sons, Inc., New York, 1953, pp. 226-228 and 787-788.

LORRAINE A. WEINBERGER, Primary Examiner C. F. WARREN, AssistantExaminer US. Cl. X.R.

1. A WATER-SOLUBLE MONOAZO DYESTUFF OF THE FORMULA